Nitrobenzylanilin sulfonic acid and process of making same.



NITED STATES PATENT OFFICE.

BENNO HOMOLKA, OF FRANKFORT-ON-THE-MAIN, AND AUGUST STOCK, OF

I-IocHsT ON THE MAIN, GERMANY,

ASSIGNORS TO THE FARBW'ERKE, I

MANY.

NITROBENZYLANILIN SULFONICACID AND PROCESS OF MAKING SAME.

SPECIFICATION forming part of Letters Patent N 0. 648,261, dated April 24, 1900. Application filed December 15, 1897- Serial No. 662,028. (Specimens) To all whom it may concern.-

Be it known that we, BENNO HOMOLKA, doctor of philosophy, a citizen of the Empire of Austria-Hungary, residing at Frankfort-onthe-Main, and AUGUST STOCK, doctor of philosophy, a citizen of the Empire of Germany, residing at Hochst-on-the-Main, Germany, have invented certain new movements in the Manufacture of Orth'o and to Para Nitrobenzylanilin Sulfonic Acids and their Homologues, (for which we have obtained Letters Patent in England, No. 15,890, dated July 3, 1897, andin France,No. 260,329, dated October 10, 1896,) of which the follow- 15 ing is a description.

This invention relates to the production of ortho-and para-nitrobenzylanilin and its homologues.

We have found that by the action of ortho- 20 or paranitrobenzylchlorid upon the sulfonic acids of anilin and its homologues in the presence of fixed alkali, alkali corbonate or acetate, or alkaline earths orammonia the nitrobenzylanilin, sulfonic acids or their homo- 2 5 logues corresponding to the simplest typical formula may easily be obtained with a good yield:

and useful Im-- Nitro-benzylchlorid, Toluidinsulfonic (orthoor para-.) acid.

Nitrobenzyltoluidinsulfonic acid, Chlorid of Acetic (sodium salt.) sodium. acid.

0H,. 01 NH,

+0 11, +NH No Nitro-benzylchlorid, Xylidinsulfonic acid, Ammo- (orthoor para-.) (sodium salt.) nia.

CH NH 0 H 3 O H +NH .HCl.

NO NaO S Nitrobenzyl-Xylidinsulfonic acid, (sodium salt.)

The nitrobenzylchlorids requisite for our process may be employed as such in a pure state or in form of such mixtures of nitrobenzylchlorid and nitrotoluene as are easily 65 Water.

Sodium acetate.

Sal-ammomac.

30 benzyl amlm obtained by partial chlorination of the nitroaccordingto the followingchemicalequations: t m t a hi h temperature If one CH 01 NH crates, for instance, in thedatter case, with 1 O H C H 2 +NaOH such a mixture contalning nitrobenzylchlorid 4 6 O Na and nitrotoluene 1n about molecular propor- 7o 35 Nitrobeuzylchlirid Anilinsulfoni acid Sodium Hons he above equatlon (1) undergoes the (orthoor para-.) (sodium salt.) hydroxid. O OWIHg Change: 01-1,.01 0H, NH,

0 H, +o,H +o,n +NaOH: I 2 N0 S0,.Na

Nitro-benzylchlorid, Nitrotoluene, Anilin sulfonic acid, Sodium (orthoor para-.) (ortho or para-.) (sodium salt.) hydroxid. The mixture of nitrobenzylchlorid and nitrotoluene obtained by partial Y chlorination of nitrotoluene.

CH -NI-I on, 0 H, o,H,+o,H, +NaOl-+H,O.

No,Nao,s No,

N itrobenzyI-anilin sulfo acid,

(sodium salt.)

+ nitrotolueue gg ii Water.

9, l 'eea-eei I The thus-regenerated nitrotoluene may easily be separated as the only constituent of the product of reaction which is insolublein wa ter. I.-Manafactare of nitrobenzylariilirisalforiic acids and their homotogaes from pure hitrobenzylchloridL In a vessel providedwith an agitator and an inverted condenser 17.1'

kilos or nitrobenzylchlorid (orthoor para) 'are heated with a solution of twenty kilos anilinsulfonate of sodium and ,5.3, kilos of anhydrous sodium carbonate in about one hundred liters of water, while stirring well to 60 to 100 centigrade until the nitrobenzylchlorid has completely disappeared. The

yellow-colored solution containing the sodium salt of the nitrobenzylanilin sulfonic acid is 1 mixed with a diluted mineral acid, Whereupon the nitrobenzylanilinsulfonic acid sepa rates partly already in the heat and completely 1n II.-ll[anafactare of the nitrobeneylanitins-alfonic acids and their homologaes from the mixtures of nitrobenzylchlorid arid 'nitrotolaene obtained by partial chlorination of nitro.--

tolaenes at a higher temperatare.-A vessel similar to that of the. previous example is, for instance, filled with 34.2 kilos of amixture of about equal parts of nitrobenzylchlorid (orthoor para-) and nitrotoluene (orthoor para-) as is obtained by partial chlorination ofnitrotoluene (orthoor'para-) and twenty kilos of anilinsulfonate of sodium and 5.3

' kilos of anhydrous sodium carbonate dissolved in about one hundred liters of water.

The whole'is brought to boil for some hours, when the nitrobenzylchlorid as in Example I,

' combines with the anilinsulfonate salt and is dissolved, while the nitrotoluene remains behind undissolved and may be removed by means of a tap or a siphon;

yellow aqueous solution of the nitrobenzyl anilinsulfonate salt is now treated exactly as in Example I.

.In both of the above examples the anilinsulfonic acids may We proceed, for instance, as follows: i

the cold asa yellowish crystalline powder.

The remaining equivalent quantities T of toluidinsulfonic acids, xylidinsulfonic acids,or naphthylaminsulfonic acids, and, further, may be substituted, as mentioned above, the sodium carbonate by the equivalent quantities of other fixed alkali, alkali carbonate or acetate, alkalineearths or ammonia;

The nitrobenzylanilinsulfonic acids and their homologues thus obtained are yellowish crystalline powders little soluble in cold water, more readily soluble in hot water, soluble with great difficulty in alcohol, insoluble in ether, benzene, toluene, xylene, chloroform, and ligroin, and soluble in dilute alkalies with a yellowish color. I

The new compounds serve for the manufacture ofnitrobenzaldehyde as required in the anilin-dye industry.

Having now described we claim isr 1. The herein-described process of producing. nitrobenzylanilinsultonic acids, which consists in heating nitrobenzylchlorid, where the nitro group is in orthoor paraposition, with-an aqueous solution of a salt of anilinour invention,- what sullonic acid in the presence of alkaline'subbe substituted by the 

